Coiled-Tubing Fluid-Lubricant Composition and Related Methods

ABSTRACT

A method for performing a coiled-tubing process, the method having the steps of performing a coiled-tubing process using a fluid-lubricant composition that includes: a sulfurized component, and a chlorinated component, wherein the sulfurized component is a sulfurized C8 to C14 olefin, wherein the chlorinated component is a chlorinated fatty ester, a chlorinated paraffin, or a chlorinated olefin; and introducing the fluid-lubricant composition into a subterranean wellbore casing.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims priority to U.S. provisional patent application Ser. No. 62/789,697 filed on Jan. 8, 2019 and titled, “Chlorinated Lubricants and the Blend of Sulfurized and Chlorinated Olefins and Fatty Esters as Effective Lubricants for Coiled-Tubing (CT) Subterranean Drilling of Oil-Gas Exploration Application.” This patent application also claims priority to U.S. provisional patent application Ser. No. 62/883,292 filed on Aug. 6, 2019 and titled, “Chlorinated Lubricants and the Blend of Sulfurized and Chlorinated Olefins and Fatty Esters as Effective Lubricants for Coiled-Tubing (CT) Subterranean Drilling of Oil-Gas Exploration Application.” The subject matter of both provisional patent applications is incorporated by reference into this application.

BACKGROUND OF THE INVENTION

The use of lubricants in coiled-tubing processes is well known, and a non-limiting example of a known coiled-tubing process that employs a lubricant within the wellbore casing is coiled-tubing drilling for subterranean oil-and-gas exploration.

BRIEF SUMMARY OF THE INVENTION

A method for performing a coiled-tubing process, the method having the steps of performing a coiled-tubing process using a fluid-lubricant composition that includes: a sulfurized component, and a chlorinated component, wherein the sulfurized component is a sulfurized C8 to C14 olefin, wherein the chlorinated component is a chlorinated fatty ester, a chlorinated paraffin, or a chlorinated olefin; and introducing the fluid-lubricant composition into a subterranean wellbore casing.

A method for performing a coiled-tubing process, the method having the steps of performing a coiled-tubing process using a fluid-lubricant composition that includes: a chlorinated fatty ester, a chlorinated paraffin, or a chlorinated olefin; and introducing the fluid-lubricant composition into a subterranean wellbore casing.

Embodiments are generally directed to coiled-tubing fluid-lubricant compositions and related methods. Using the fluid-lubricant-composition embodiments in coiled-tubing applications causes improved coiled-tubing-process field performance relative to coiled-tubing methods that use known coiled-tubing lubricants. Using the coiled-tubing fluid-lubricant-composition embodiments enable coiled tubing to travel greater distances within a wellbore casing relative to the distances that can currently be reached by using known coiled-tubing lubricants. Use of the fluid-lubricant-composition embodiments allow coiled tubing to travel distances within a wellbore casing that are 50 to 110% farther than the distances that can be reached by using known coiled-tubing lubricants. Coiled-tubing fluid-lubricant-composition embodiments enable coiled tubing to reach distances within the wellbore casing ranging from 10,000 feet to 25,000 feet. The relatively farther coiled-tubing distances that can be achieved because of the fluid-lubricant-composition embodiments are at least in part believed to be due to the increased friction reduction (relative to the friction reduction of known coiled-tubing lubricants) between a wellbore-casing interior wall and the coiled tubing.

Compared to known coiled-tubing lubricants, the coiled-tubing fluid-lubricant-composition embodiments are 50 to 100% more effective in reducing friction generated by sliding steel against steel surfaces. The coiled-tubing fluid-lubricant-composition embodiments generate friction reductions ranging from 40 to 55% or more compared to 20 to 25% obtained from the current commercial lubricants or additives.

DETAILED DESCRIPTION OF THE INVENTION

Coiled-tubing fluid-lubricant embodiments are directed to fluid-lubricant compositions and their use as lubricants in coiled-tubing methods by introducing the compositions into a subterranean wellbore casing. In embodiments, the coiled-tubing fluid-lubricant compositions include: a sulfurized component, and a chlorinated component, wherein the sulfurized component is a sulfurized C8 to C14 olefin, wherein the chlorinated component is a chlorinated fatty ester, a chlorinated paraffin, or a chlorinated olefin. In other embodiments, the coiled-tubing fluid-lubricant compositions include a chlorinated component, wherein the chlorinated component is a chlorinated fatty ester, a chlorinated paraffin, or a chlorinated olefin.

Embodiments are directed to fluid-lubricant compositions that include a sulfur-containing or sulfurized compound. Useful sulfur-containing compounds include compounds having carbon-chain lengths ranging from C8 to C20. In embodiments, useful sulfur-containing compounds have carbon-chain lengths that are C8, C10, C12, C14, C16, C18, or C20. In embodiments, useful sulfur-containing compounds have carbon-chain lengths that are C10, C12, C14, or C16. In embodiments, the sulfur-containing compound has a carbon-chain length of C8. In embodiments, the sulfur-containing compound has a carbon-chain length of C10. In embodiments, the sulfur-containing compound has a carbon-chain length of C12. In embodiments, the sulfur-containing compound has a carbon-chain length of C14. In embodiments, the sulfur-containing compound has a carbon-chain length of C16. In embodiments, the sulfur-containing compound has a carbon-chain length of C18. In embodiments, the sulfur-containing compound has a carbon-chain length of C20. In embodiments, the sulfur-containing compound has a carbon-chain length ranging from C8 to C14. In embodiments, the sulfur-containing compound is a sulfurized olefin having a carbon-chain length ranging from C8 to C14.

In embodiments, a useful sulfur-containing compound is the reaction product of a process that reacts either: i) sulfur and an olefin, or ii) sulfur and a fatty ester. Useful olefin reactants include both alpha and non-alpha olefins; wherein alpha can be understood to have its common meaning that a double bond is located in the primary position. In other embodiments, useful olefin reactants are internal or branched olefins. Useful fatty-ester reactants include oleates and linoleates. Additional useful fatty-ester reactants include soybean oil, soybean-based methyl esters, canola oil, canola-based methyl esters, triglyceride, animal fats, and lard oils. In embodiments, the fatty-ester reactant is a canola-based methyl ester. In embodiments, the fatty-ester reactant is a soy-based methyl ester.

In embodiments, the sulfur-containing compound has an amount of sulfur ranging from 10% to 50% by weight relative to the total weight of the compound. In other embodiments, the sulfur-containing compound has an amount of sulfur ranging from 10% to 35% by weight relative to the total weight of the compound.

Additional useful sulfur-containing compounds include: sulfurized (10% S) canola-based methyl esters, sulfurized (15% S) canola-based methyl esters, sulfurized (22% S) C9 olefins, sulfurized (35% S) C9 olefins, sulfurized (20%) C10 olefins, sulfurized (38%) C10 olefins, sulfurized (18% S) C12 olefins, sulfurized (28% S) C12 olefins, sulfurized (16% S) C14 olefins, sulfurized (25% S) C14 olefins, sulfurized (20%) C16 olefins, sulfurized (32%) C16 olefins, sulfurized (12% S) C18 olefins, and sulfurized (20% S) C18 olefins. In the immediately above list of sulfur-containing compounds, the “sulfurized (X %) CN compound classification” means that the compound(s) is X % sulfur by weight relative to the total weight of the compound and that the compound has a specific number of carbon atoms.

In another embodiment, a useful sulfur-containing compound is sulfurized alkyl succinic anhydride.

As mentioned above, the fluid-lubricant-composition embodiments include at least one sulfur-containing compound. In embodiments, the fluid-lubricant composition includes 1% to 10% by weight one-or-more sulfur-containing compounds, relative to the total weight of the fluid-lubricant composition. In other embodiments, the fluid-lubricant composition includes 1% to 2% by weight one-or-more sulfur-containing compounds, relative to the total weight of the fluid-lubricant composition.

Embodiments allow for any sulfur-containing compound taught herein to be used alone or in combination with any other sulfur-containing compound taught herein.

In embodiments, the chlorinated component is a chlorinated fatty ester, a chlorinated paraffin, or a chlorinated olefin.

Additional fluid-lubricant-composition embodiments include both a sulfur-containing compound and an emulsifier. An emulsifier can be understood to have its ordinary meaning that is generally a compound or substance that stabilizes an emulsion by preventing liquids from separating. In embodiments, the emulsifier can be any known non-ionic emulsifier. In embodiments, useful emulsifiers include a polyethylene glycol, a polyethylene glycol ester, or combinations thereof. Useful amounts or weight percentages of emulsifier within the sulfur-containing fluid-lubricant can be determined by a person of ordinary skill in the art without having to exercise undue experimentation.

In embodiments, the coiled-tubing fluid-lubricant-composition embodiments reduce the friction generated by steel sliding against steel surfaces by at least 40%. In embodiments, the coiled-tubing fluid-lubricant-composition embodiments reduce the friction generated by steel sliding against steel surfaces by at least 45%. In embodiments, the coiled-tubing fluid-lubricant-composition embodiments reduce the friction generated by steel sliding against steel surfaces by at least 50%.

The sulfur-containing coiled-tubing lubricant-composition embodiments can be used in the same manner that currently known coiled-tubing lubricants are used in coiled-tubing methods. The sulfur-containing coiled-tubing lubricant-composition embodiments can be introduced into a wellbore casing in the same manner that currently known coiled-tubing lubricants are introduced into a wellbore casing. When conducting coiled-tubing methods or operations, useful amounts of the sulfur-containing coiled-tubing lubricant-composition embodiments can be discovered by persons of ordinary skill in the art without having to exercise undue experimentation.

Non-limiting examples of useful sulfur-containing fluid-lubricant embodiments are presented below in the Examples section in Tables I and II.

EXAMPLES

TABLE I List of Tested Coiled-Tubing Lubricants COILED-TUBING (CT) LUBRICANTS Lubricant I: Sulfurized (10% S) canola-based methyl esters Lubricant II: Sulfurized (15% S) canola-based methyl esters Lubricant III: Sulfurized (20% S) C-10 olefins Lubricant IV: Sulfurized (38% S) C-10 olefins Lubricant V: Sulfurized (20% S) C-16 olefins Lubricant VI: Sulfurized (32% S) C-16 olefins

Canola-based methyl esters which primarily consist of methyl oleate (one double bond or one site of unsaturation) and methyl linoleate (two double bonds or two sites of unsaturation). These unsaturated fatty esters and relatively short-chained olefins were chosen to illustrate this new class of CT lubricants in order to have sufficient unsaturation sites on the chemical structures of the raw material(s) to be sulfurized or for sulfide linkages to be formed, especially at higher levels of sulfur percentage than 10-12% S which is typical for a non-active sulfurized additives. The higher-than-12% S renders a lubricant or additive much more reactive to a metal surface such as copper or steel to form a metallic sulfide coating which acts as a sacrificial go-between, an interlayer to separate two rubbing or sliding metallic surface resulting in less welding, deformation, and in the case of CT process, much less friction and drag. All sulfurized compounds were made by a conventional sulfurization process at around 160-185 C with flour sulfur and fatty esters or olefins with heating and exotherm.

TABLE II General Coiled-Tubing Lubricant- Composition Formula Used in Table I Tap water 350 g Xanthan gum 0.5 g PAC or Poly anionic cellulose 0.5 g NaOH bead 0.1 g Polyethylene glycol (MW = 600) tallate esters 0.65 g NaCl or table salt 12 g Rev-Dust or calcium montmorillonite 5.0 g Sulfurized Compound(s) from Table I, i.e., 5.0 g Lubricant I, II, III, IV, V, or VI

Tap water might be replaced with brines of different concentrations of salts ranging from 1 to 20%; salts can be NaCl, KBr, KCl, etc. Xanthan gum and PAC or poly-anionic cellulose are water-dispersible thickeners which yield a gel strength and viscosities for the formulated fluid. These polymers were chosen instead of the conventional poly-acrylic amides to exclude the minor known lubricating contribution coming from water-dispersible amides. Caustic beads are present to buffer the fluid to a basic level of pH greater than 7. Polyethylene glycol or PEG esters act as an emulsifier effective enough to disperse non-soluble or non-dispersible highly sulfurized lubricants in water or diluted brine mixtures. NaCl or other salts are used to render some shale inhibition or protection for the integrity of wellbore. Rev-Dust or calcium montmorillonite is added as a simulation for cuttings of actual drilling process. These unreactive fine clay particles will simulate an abrasiveness of drilling into subterranean formations and inner surfaces of casing and wellbore. And the finally added ingredient is the novel highly sulfurized lubricant and its counterparts.

Testing Method—Description and Conditions

Since CT drilling is linear drilling meaning the drill bits are thrusted forward into a well-bore in one linear dimension instead of the rotary mechanism of a conventional drilling, Draw-Bead tester were used to measure the friction reduction (% FR) or the effectiveness of a tested lubricant instead of Ofite meter which is conventionally used to measure % FR of lubricant in a drilling fluid, due to the fact that Ofite test is designed to measure rotary mechanism only.

A steel trip coated with tested CT fluid which contains 1 wt. % of novel lubricant is sandwiched and drawn through a set of hardened-steel dies. The dies are heated to 200 F temperature The steel strip is cleaned and de-burred then is coated with the CT fluid to be tested. The coated strip is placed vertically in a vice and raised in between two dies. The dies apply 500 psi to the strip and the strip is drawn between the dies. As the strip is drawn, the force needed to pull the strip through the dies is plotted on the x-y plotter. Force is calculated from this plot. A total of two strips are run per sample. And percent's of friction reduction or % FR is calculated based on the difference in the pulling forces used for the tested fluid versus the standard fluid which can be a blank fluid containing no lubricant.

Testing Results and Discussion:

TABLE III Friction Reduction As a Function of Sulfur Level in Coiled-Tubing Lubricant Compositions % FRICTION COILED-TUBING (CT) FLUIDS REDUCTION Blank CT Fluid, no lubricant  0% 1% Known Commercial CT Lubricant 23% 1% sulfurized (10% S) canola-based methyl esters 40% (Lubricant I) 1% sulfurized (15% S) canola-based methyl esters 48% (Lubricant II) 1% sulfurized (20% S) C-10 olefins (Lubricant III) 40% 1% sulfurized (38% S) C-10 olefins (Lubricant IV) 55% 1% sulfurized (20% S) C-16 olefins (Lubricant V) 42% 1% sulfurized (32% S) C-16 olefins (Lubricant VI) 55%

Blank coiled-tubing fluid contains no lubricant; its performance or required pulling hydraulic force was used as a standard. The fluid containing 1 wt. % of well-known commercial CT lubricant was added into the mix to see if its performance meaning established 20 to 25% friction reduction from the field could be illustrated by the Draw-Bead test; and it did quite well with 23% friction reduction (FR). We can see clearly that the FR is the function of the sulfur level in all sulfurized additives or lubricants; a higher sulfur level resulted in a greater friction reduction percent. And the increases in FR of the novel highly-sulfurized lubricants are about 70% to 140% of the commercial CT lubricants, more than sufficient for BHA of a coiled tubing apparatus to reach the entire length of a horizontal wellbore or lateral production zone.

Embodiments illustrate the advantages of using the chlorinate lubricant or the additive blends of sulfurized and chlorinated additives such as sulfurized fatty esters or olefins and chlorinated fatty esters or paraffins or olefins as a friction-reducing lubricants in coiled-tubing or CT drilling applications.

Coiled-Tubing Drilling Fluid Formula:

Tap water 350 g Xanthan gum 0.5 g PAC or Poly anionic cellulose 0.5 g NaOH bead 0.1 g Polyethylene glycol (MW = 600) tallate esters 0.65 g NaCl or table salt 12 g Rev-Dust or calcium montmorillonite 5.0 g Novel sulfurized-chlorinated lubricant blend 5.0 g

Testing Method:

Since CT drilling is linear drilling meaning the drill bits are thrusted forward into a well-bore in one dimension instead of the rotary mechanism of a conventional drilling, Draw-Bead tester were used to measure the friction reduction (% FR) or the effectiveness of a tested lubricant instead of Ofite meter which is conventionally used to measure % FR of lubricant in a drilling fluid, due to the fact that Ofite test is designed to measure rotary mechanism only.

Testing Description and Conditions:

A steel strip coated with tested CT fluid which contains 1 wt. % of novel lubricant is sandwiched and drawn through a set of hardened-steel dies. The dies are heated to 120 F temperature. The steel strip is cleaned and de-burred then is coated with the CT fluid to be tested. The coated strip is placed vertically in a vice and raised in between two dies. The dies apply 500 psi to the strip and the strip is drawn between the dies. As the strip is drawn, the force needed to pull the strip through the dies is plotted on the x-y plotter. Force is calculated from this plot. A total of two strips are run per sample. And percent's of friction reduction or % FR is calculated based on the difference in the pulling forces used for the tested fluid verse the standard fluid which can be a blank fluid containing no lubricant.

Testing Data or Results:

% Friction Reduction, 1% Lubricant in Coiled-Tubing Fluids:

% FR % FR COILED-TUBING (CT) CT Fluid made CT fluid made with FLUIDS produced water fresh water Blank CT Fluid, no lubricant 0 0 1% Canola oil in CT fluid +5.3% +32.8% 1% sulfurized methyl oleates, +44.4% +39.3% 10% S, in CT fluid 1% sulfurized C-12 olefin, +51.6% +49.2% 35% S, in CT fluid 1% blend of 35% S C-12 olefin +21.1% +78.7% and 54% Cl paraffins in CT fluid 1% 54% Cl chlorinated +15.2% +49.2% paraffins

All sulfurized compounds were made by a conventional sulfurization process at around 160-185 C with flour sulfur and fatty esters or olefins with heating. All chlorinated lubricants were made with convention chlorination with paraffins wax or olefins, and with chlorine gas, with heating or without heating to 60-135 C. 

1. A method for performing a coiled-tubing process, the method comprising the steps: performing a coiled-tubing process using a fluid-lubricant composition that includes: i) a sulfurized component, and ii) a chlorinated component; wherein the sulfurized component is a sulfurized C8 to C14 olefin; wherein the chlorinated component is a chlorinated fatty ester, a chlorinated paraffin, or a chlorinated olefin; and introducing the fluid-lubricant composition into a subterranean wellbore casing.
 2. The method of claim 1, wherein the fluid-lubricant composition also includes an emulsifier component.
 3. The method of claim 2, wherein the emulsifier component is a polyethylene glycol or a polyethylene glycol ester.
 4. The method of claim 1, wherein the fluid-lubricant composition reduces the friction generated by steel sliding against steel surfaces by at least 40%.
 5. The method of claim 1, wherein the sulfurized component is a sulfurized (22% S) C9 olefin, a sulfurized (35% S) C9 olefin, a sulfurized (20%) C10 olefin, a sulfurized (38%) C10 olefin, a sulfurized (18% S) C12 olefin, a sulfurized (28% S) C12 olefin, a sulfurized (16% S) C14 olefin, or a sulfurized (25% S) C14 olefins.
 6. A method for performing a coiled-tubing process, the method comprising the steps: performing a coiled-tubing process using a fluid-lubricant composition that includes: a chlorinated fatty ester, a chlorinated paraffin, or a chlorinated olefin; and introducing the fluid-lubricant composition into a subterranean wellbore casing.
 7. The method of claim 6, wherein the fluid-lubricant composition also includes an emulsifier component.
 8. The method of claim 7, wherein the emulsifier component is a polyethylene glycol or a polyethylene glycol ester.
 9. The method of claim 6, wherein the fluid-lubricant composition reduces the friction generated by steel sliding against steel surfaces by at least 40%. 